Anthraquinone dyes

ABSTRACT

1-AMINO-4-HYDROXYANTHRAQUINONES CONTAINING IN THE 2-POSITION A CARBOXYL GROUP ESTERIFIED BY DIOLS HAVING FOUR TO 10 CARBON ATOMS.

United States Patent [72] Inventor Karl Maler Ludwigshafen am Rhine, Germany [2!] Appl. No. 720,353 [22] Filed Apr. 10, 1968 [45] Patented Dec. 14, 1971 [73] Assignee Badlsche Anilin-& Soda-Fabrlk Aktlengesellschaft Ludwigshafen am Rhine, Germany a 32 Priority Apr. 14, 1967 Germany 311 Pl644468.l

[54] ANTHRAQUINONE DYES 2 Claims, No Drawings [52] U.S. Cl 260/376 [5 1] Int. Cl C09b 1/50 [50] Field of Search. 260/376 Erikhov et al., As cited in Chem Abstracts, 67, 100983, (1967).

Primary Examiner- Lorraine A. Weinberger Assistant ExaminerE. Jane Skelly Attorney-Johnston, Root, OKeeffe, Keil, Thompson &

Shurtleff ABSTRACT: l-amino-4-hydroxyanthraquinones containing in the 2-position a carboxyl group esterified by diols having four to 10 carbon atoms.

ANTHRAQUINONE DYES This invention relates to new anthraquinone dyes which are outstandingly suitable for dyeing. or printing synthetic textile material. The new dyes have the formula:

T he new dyes are prepared by reacting l-amino- 4-hydroxand yanthraquinone-Z-carboxylic acid derivatives of this carboxyl- I The 1-amino-4-hydroxyanthraquinone-2-carboxylic acid or derivative of this acid is reacted with the diol by a conventional method of esterification, for example by heating the lamino-4-hydroxyanthraquinone-Z-carboxylic acid with the appropriate diol in the presence of an esterification catalyst at a temperature of from 1 to 130 C. It is advantageous to use an excess, for example four to 10 times the weight of diol with reference to the anthraquinone carboxylic acid.

The carboxyl group in the 2-position in the 1-amino-4- hydroxyanthraquinone-2-carboxylic acid may also be esterified by first converting the acid into the corresponding isatoic anhydride with phosgene followed by reaction of the anhydride with the appropriate diol at a temperature of from 130 to 160 C. The reaction may be carried out in an excess of diol or in a solvent which is inert under the reaction conditions, such as chlorobenzene or xylene, and in the presence of a small amount of an organic base such as pyridine. The said isatoic anhydride may be prepared for example by heating the anthraquinone carboxylic acid with phosgene in a solvent which is inert under the reaction conditions such as chlorobenzene or dichlorobenzene at 130 to 150 C.

The new dyes are outstandingly suitable for dyeing or printing synthetic textile material, particularly linear polyester tex- Q1 in which X denotes a saturated hydrocarbon radical having superior to the dyes known from U.S. Pat. No. 2,823,212 especially in fastness to heat setting and light fastness, and superior to the dyes known from British Pat. No. 721,283 in the color strength of the dyeings obtained on polyester cloth.

The invention is illustrated by the following examples. The parts specified in the examples are parts by weight.

EXAMPLE 1 Twenty parts of -l-amino-4-hydroxyanthraquinone-2-carboxylic acid is heated with 80 parts of hexanediol-( 1,6) and 4 parts of p-toluene-sulfonic acid for 18 hours at 120 C. and then allowed to cool. One hundred parts of methanol is added, the whole is cooled and the residue is suction filtered and washed with methanol. Twenty-one parts of the dye having the 20 formula:

0 NHz H l OOH EXAMPLE 2 One hundred pans of isatoic anhydride (prepared identical 1-amino-4-hydroxyanthraquinone-2-carboxylic acid and phosgene) is heated with hexanediol-( 1,6) under reflux in 300 parts of xylene and in the presence of 5 parts of pyridine for 4 to 5 hours. The whole is suction filtered while hot, the filtrate is allowed to cool and the dye is suction filtered. Eighty-five parts of dye is obtained which is identical with the dye obtainable according to example 1. Similar dyes are obtained when the diols specified in the following table are used. The following abbreviations are usedin the table: E Example No.;

m.p. Melting point of the dye in C.; Solvent= solvent used for the recrystallization.

TABLE E D101 M.P. Solvent 3 Butanedi01-(1,3) .i 4. Butanedio1-(1,4) 5 2,2dimethy1propanediol-(1,3)- 6. 2,2-diethy1pr0panedio1-(1,3) 7. 2-buty1-2-ethylpropanediol-(1,3) 8. 2,2,4-trlmethy1pentanedio1-(1,3) 9. Decanadiol-(1,l0) 10. 2,2-dimethylhexanedio1-(1,3). 11- Hexahydroterephthalyl alcohoL...

149-150 Benzene.

Toluene Do. Benzene. Toluene.

D0. Butanol. Chlorobenzene.

We claim: ,7 ,1; vnt i qvs W having formula 5 in which X denotes a saturated hydrocarbon radical having four to 10 carbon atoms. V. Tbid eh yias e srm 

2. The dye having the formula: 